Anthraquinone vat dyestuffs



a 2,741,621 Ice Patented Ap 1956 United States Patent 1 2 2,741,621derivatives of dicarboxylic acids of the formula (3) ANTHRAQUINONE VATDYESTUFFS B000 0 I. 0 Eduard Moergeli and Adolf Emil Siegrist, Basel,and 5 GM c o c ol, ln,..ooon

Kurt Hoelzle, Liestal, Switzerland, assignors m Ciba I t, L M 1 Limited,Basel, Switzerland, a Swiss firm V in which m and I: each represent awhole number not N0 Drawmg- ,APPhcafion July 1934 greater than 2.Valuable dyestufis are obtained especially Senal 445159 with thosederivatives of dicarboxylic acids of the Forl i prigrity applicationSwitzerland July 27, 1953 mula 3 which contain as radicals of theconstitution 8 Claims. ((1260-3075) H000 and C4n-2Hh-CO0H This inventionprovides anthraquinone vat dyestufis which, like, for example, thedyestufi of the formula benzene carboxylic acid radicals bound to theoxdiazole i) it contain an acyl radical derived from a dicarboxylic acid25 ring in para-position relatively to the carboxyl group,

containing at least one oxdiazole ring, and in which the that is to say,derivatives of dicarboxylic acids of the CO- groups of the acyl radicalare bound to amino- Formulae 5 and 8 below.

anthraquinone radicals. The dicarboxylic acids can be prepared, forexample,

This invention also provides a process for the manuby treating acompound of the formula facture of the above new dyestuffs, bycondensing two With an agent Capable of Splitting Ofi Water, and thenmolecular proportions of an aminoanthraquinone or one hydrolyzing thecarboxylic acid ester groups. The symmolecular proportion each of twodifierent aminoanthra- [1018 and n have the gs gi n in quinones with onemolecular proportion of a reactive Formula 2 above, and in at least oneof the radicals R, derivative of a dicarboxylic acid in such manner asto R1 and R2 the carbon atom, which is bound to the radiform bilaterallycarboxylic acid anthraquinonyl-amide Cal co g The g p is Present in asystem groups, wherein the dicarboxylic acid derivative used is ofconjugated double bonds.

derived from a dicarboxylic acid containing at least one A5 examples ofdicafboxylic acids, most of which are oxdiazole ring. advantageouslyprepared in this manner, there may be As reactive derivatives of theaforesaid dicarboxylic mentioned the following compounds: acids therecome into consideration, especially their dihalides and among thelatter, preferably the dichlorides. bls [4 cal-boxy phenyl (1 )1oxdlazole of the These halides can be obtained in known manner from 1the dicarboxylic acids. It is especially advantageous to (5) prepare thedichlorides with the aid of thionyl chloride HOOCOC CO-CQOH in an inertsolvent or diluent, as the mixture so obtained can be used, after theformation of the acid halide and distillation of the excess of thionylchloride, directly for formulaZiS-bis-[3'-carboxy-phenyl-(1')l-lz3z4-oxdiazole of the the condensationwith the aminoanthraquinones. formula There are advantageously usedderivatives of dicar- 0 boxylic acids of the constitution Hood 0 c 00011I II (2) O 0 .N

HOOCR1-("3 fi RM-fi tfi -ns-coofl N L N'NJ-l 2:5 bis [4" carboxydiphenyl (4')] 1:314-

in which R, R1 and R2 represent any desired organic OXdiflZOle 0f e rula f hi h H t m of co 2 [4' carboxy phenyl (1')] 5 [5" (4"' car- 2; 2.con i 2 2 25 1 d n boxy phenyl (1"') l":3":4" oxdiazolyl (2)1- Jugae one on f 15 cenjug? ,f e 1:3:4-oxdiazole of the formula ble bonds of theoxdiazole mg to which 1t 1s attached, (8) and in which m and 22represent lower whole numbers,

0 O advantageously a whole number not greater than 2. HOOC-C -C fi fi(HOC OOH Good results are obtained in the present process with 2 [3carboxy phenyl (1')] 5 [5" 3"' carboxy phenyl) (1) l:3":4" oxdiazolyl(2")]- 1:3:4-0xdiazole of the formula 1 13' .carboxy phenyl) 1"')1',:3':4- oxdiazolyl (2')] 4 5" (3"" carboxy phenyl)-(1")-(1":3":4"-oXdiazolyl-(2")]-benzene of the formula 11) o o HO 0 o 000-0 o 011 u u u N---N N N .COOH

and 2' [4" car-boxy phenyl (1")1 1:3':4'-

oxdiazolyl-(5')-,8-.acrylic acid of the formula The reactivedicarboxylic acid derivatives are reacted either withaminoanthraquinones, advantageously aaminoanthraquinones, for examplel-aminoanthraquinone itself, or with a-aminoanthraquinones containingfurther substituents. Among the latter valuable dyestutfs are Obtainedabove all with I-aminO-S-arOylaminO-anthraquinones, particularly 1-amino5 benzoylaminoanthraquinones of which the benzoyl radicals may containhalogen atoms as substituents, suchas iodine or bromine or especiallychlorine and/or fluorine. As examples there may be mentioned1-amino-5-benzoylamino-, 1-arnino-5-(4- chlorobenzoylamino)-, l amino5-(2'-fluorobenzoylamino) and 1-amino 5-(2 fluoro-4 or-5chlorobenzoylamino) -anthraquinone.

'When the :roaotion is .carried .out with .anthraguinones which containtwo free amino groups, in whic case 1:5-diaminoanthraquinone isadvantageously used, the free amino groups stillpresent in theproductsso obtained are advantageously also acylated, the acylating agents beingderived from monocarboxylic acids, advantageously monocarboxylic acidsof the benzene series. 1 thi @9 nection there come into considerationprima l halides of those benzene carboxylic acids which are capable ofyielding the radicals mentioned in the preceding paragraph.

The reactions of thegpresentprocess, that is to say, the reaction of thed-icarboxylic acid derivatives with the aminoanthraquiuones and thesubsequent further acylation with an acylating agent derived from amonocarboxylic acid which may be carried out if desired, areadvantageously conducted in solvents or diluents, preferably those ofhigh boiling point such as -monoch,lorobenzene, dior tri-chlorobenzenes,nitrobenzene or naphthalene, at a raised temperature, for example, he

tween about 100 C. and the boiling point of the solvent or=diluentnsed.The above'rnentioned reaction products obtainable from'l:5-diaminoanthraguinone and the dicarboxylic acids in the firststage,for which purpose it is of advantage to bring the1:5-diaminoanthraquinone and dicarboxylicacid derivative into reaction-ina molecular ratio'ranging from 2:1 to 3:2, can :be further .acylaieslwithout being isolated from the reaotion-mixture. Dyestuffs ofasymmetrical constitution are obtained when one molecular proportion ofthe dicarboxylic acid derivative is condensed with one molecularproportion of each of two amino anthraquinones.

The new vat dyestuffs of the foregoing constitution and obtainable asdescribed above, can be used in known manner as such or in the form oftheir leuco-ester salts obtainable in known manner, for dyeing orprinting a e y wide variety i fibe s o a ima n espe a ly e 0 tablecharacter, for example, wool, silk but advantageously cotton, linen,artificial silk and staple fibers of regenerated cellulose and alsosuperpolyamide fibers.

The dyeipgs and prints so produced are distinguishedby their interestingtints and good properties of fastness.

The new dyestuffs are especially valuable because they are suitable fordyeing by various methods known for vat dyestuffs (at lower or highertemperatures). Thgy are also distinguished by the fact that they yieldalone or together with other dyestuffs dyeings of good fastness tolight. In this connection there may be mentioned more especially thepure yellow-green tints which ,can be produced with known blue-greendyestuifs in admixture with those yellow dyestuffs of the presentinvention which contain twice the radical of 1-an'iinoanthraquinone orof a l-arnino-S-aroylaminoanthraquinone. In connection with theavoidance of injury to the fibers the new dyestuffs of the presentinvention are also advantageous.

The following examples illustrate the invention, the parts andpercentages being by weight unless otherwise stated and the relationshipof parts by weight to parts by volume being the same as that of thekilogram to the liter.

EXAMPLE 1 3.1 parts of 2:SPbis-i4 carboxyphenyla(l)1423:4- oxdiazole ftc v o rm la are heated with 15 parts of thionyl chloride, 0.05 part ofpyridine and 200 parts of trichlorobenzene in the courseof 1V; hoursfrom 80 Q, to the boil, while Stirring- .20 pa 9 th s en a h d t ll d nd4.6 parts of l aminoanthraquinone are added to the solutionat about 10C- Th mix is h a o and st rre or 211mm a 1 0- 19 t ol g the mixtur o 29Q. the P c p at y lo dysswfi 9f the formula 1 above is filtered off,Washed with alco- 1101 and dried; j lt dissolves in concentratedsulfuric acid with a y l ow co oration nd .dy t o f o a violet vat fastgreenish yellow tints.

By using, instead of 2:5 bis-[4'-carboxyphenyl-(1-)]- 1:3:4-oxdiazole,3.78 parts of the compound of the formula There is obtained a similaryellow dyestuff which dyes cotton from a bordeaux colored vat fastgreenish yellow .tints.

In th following ta l are s ren example o .furth dyestuffs obtainable inan exactly analogous manner from '2 mols of the anthraquinone compoundsmentioned in column I and '1 11101 of the .dicarboxylic acids given incolumn h p operties of th dye tuffs being g en in ..colm.1,1ns .III andI H In Or or of Anthraquinone components, 2 mols D yl acid, 1 1 1 zg gghydrosulfite vat 1 1-Amino-5-benzoylaminoanthraquinone-. H0 0 0 0 03yellow violet.

l l L/ O 2 1-Amlno-5 (2'-fluorbenzoylamino) anthra- H0 0 C C 0 0 doblue.

qulnone. 1$

3 1-Amino-5-benzoylaminoanthraquinone- H0 O- 0 0H .-do violet.

(12) N-N /O /O fin HOOO-Otfi c o E -O0 003 Do.

( N-N I&N

' i 5 l-Agino-S (2'-fluorhenzoylemino) snthrs. HO 0 C ('3 CCH=CHC O OHdo bordeaux.

(1 one.

o a do BOOB-O c EGO OOH do violet.

IB'-N N-N O 7 l-Amlnoanthraqninone 0 F C 0 0H .--do red violet.

( l-l-N 8 l-Amino--beuzoylamlnoanthraquinone. H0 0 -6- -O 0 0 red gr nblue.

( I IN 9 1-Amino-4-methoxyanthraquinone H0 0 O1? IOU O OH orange red.

HO 0 C o C O OH 10 l-Annnoanthraqumone 0 ([3 yellow bordeaux.

H O O C 0 C O OH l1 l-Ammo-Qbenzoylammoanthraqumone-. (I? (\fred violet.

HO 0 C C O OH 12 l-Amino-S-benzoylaminoanthraquinone ("3 0 yellowbordeaux. (a) N- HO O C C O OH 1s l-Alnino-fi- (2'-fluorbenzoyl-amino)-anthrao 0 do Do.

qumone. (6) IL! Dyestuffs yielding yellow shades on cotton are alsoobtained by condensing one mol of a dihalide of a dicarboxylic acidlisted in col. II (for example No. (5)) with one mol of a first (forexample l-amino-S-benzoylaminoanthraquinone) and one mol of a second(for example l-amino-S-(2'-fluorbenzoylamino)-anthraquinone)aminoanthraquinone.

The dicarboxylic acids specified in the table are advantageouslyprepared as follows:

Dicarboxylic acid of the Formula 5 10 parts of symmetrical4:4-dicarbethoxy-dibenzoy1 hydrazide are introduced at room temperatureinto 100 degrees with the evolution of hydrochloric acid gas. Thesolution so obtained is then heated to 50 C. in the course of 20minutes, and then introduced into a mixture of water and ice. Afterstirring the mixture for a short time, the precipitated colorlessproduct is filtered ofi and Washed free from acid. The yield is greaterthan 90 percent of the theoretical yield. The2:5-bis-[4'-carbethoxyphenyl-(1)]-lz3z4-oxdiazole so obtainedcrystallizes from aqueous dioxane in the form of needle-like lamellaemelting at 215 C.

For the purpose of hydrolysis 3 parts of the ester are boiled underreflux for one hour with a solution of 10 parts of potassium hydroxidein 50 parts of alcohol. By

parts of chlorosulfonic acid. The temperature rises a few the additionof 250 parts of water the greater part of the suspension is brought intosolution. The mixture is filtered to remove undissolved constituents andthe filtrate is acidied with a mineral. a i The p pitated 2:,5-his-[4-carboxyphenyl-(l)]-1:3:4-oxdiazole of the Formula is filtered ofi,washed and dried. There are obtained 2.3 parts of a colorless powderwhich is sparingly soluble in the usual solvents. From a large quantityof 'y-valerolactone the acid crystallizes in the form of handsomecoalesced needles, which do not melt at 360 C. The acid is easilysoluble in dilute sodium carbonate solution.

The symmetrical 4:4-dicarbetllqxy-dibenzoylhydrazide mentioned above canbe obtained, for example, by reach ing terephthalic acid monoethyl esterchloride with terephthalic aeid ethyl ester monohydrazide in pyridine orby the ion o 1 .0 of yd azine hy rat on 2 18. f terephthalic acidmonoethyl ester chloride in an inert diluent, for example, chloroform,with the addition of pyridine. The substance crystallizes fromchlorobenzene in the form of colorless crystals melting at 197-198 C.

Dicarboxylic acid of the Formula 6 Into a solution of 26 parts ofhydrazine sulfate in 384 P ts. of l u on a i g 24=19 r cent. o 503) t rea introduced, while cooling and stirring well, 6.9.7 parts ofisophthalic acid in small portions in such manner that the temperaturedoes not rise above C. The mixture is then heated in the course, of 310minutes to 55 C;., and is then stirred for 5-6 hours at 55-65 C., untilthe excess of dicarboxylic acid no longer diminishes. The whole is thenallowed to cool, the clear reaction mixture ispoured into. ice Waterwhile stirring, the precipitated condensation product is filtered offwith suction and washed several times with water.

For the purpose of purification, the condensation product may bedissolved in a cold dilute solution of sodium carbonate, freed frominsoluble constituents by filtration, and reprecipitated byacidification with a dilute mineral acid.2:5-bis-[3'-carboxyphenyl-(1')]-l:3z4-oxdiazole of the Formula 6 isobtained in the form of an almost white powder, which is easily solublein a dilute aqueous solu-. tion of sodium carbonate. An aqueous solutionof the disodium salt exhibits a bluish fluorescence when exposed toultraviolet rays.

Dicarboxyl'ic acid of the Formula 8.

10 parts of the compound of the formula melting at 269-271 C(obtainable, for example, by reacting mol of oxalyl chloride with 2 molsof terephthalic acid monoethyl ester monohydrazide or by reacting 2 molsof terephthalic acid monoethyl ester chloride with one mol of oxalicacid dihydrazide) are introduced at room temperature into 1500; parts ofchlorosulfonic acid. The mixture is then heated in the course of /2hour, to 50. C., and the reaction product is then introduced into amixture of ice and water. precipitated substance of the formula from thefiltrate in the form of a colorless gelslike precipi= tate by theaddition of a mineral acid. The precipitate is filtered off andthoroughly washed with hot water. For the purpose of purification, thedicarboxylic acid may be dissolved in a cold dilute solution of sodiumcarbonate, and reprecipitated with a mineral acid, after filtering thesolution to remove a small amount of impurities. The

dried acid is a colorless powder which'does not melt when heated up to360 C.

Dicarboxylic acid of the Formula I2 10 parts of the compound of theformula (15 c o-cu 350200000 ONHN Ll o on are introduced at roomtemperature into 100 parts of chlorosulfonic acid, whereupon thetemperature rises slightly. course of /2 hour to C., cooled and thenpoured on to a mixture of ice and water. The precipitated product of therearrangement having the formula is filtered off and washed free fromacid with water. It crystallizes from alcohol in the form of long silkyneedles melting at 189 C.

In order to hydrolyze the ester group 6 parts of the product are boiledwith 50 parts of alcohol and 15 parts the acid is dissolved in a colddilute solution of sodium carbonate, and reprecipitated with a mineralacid, after filtering the mixture to improve impurities.

The compound of the Formula 15 can be obtained by condensingterephthalic acid ethyl ester monohydrazide with maleic anhydride. Thiscondensation is advantageously carried out in an inert diluent, forexample,

benzene or chlorobenzene. The condensation product crystallizes fromalcohol in the form of small colorless coalesced needles melting at166-l67 C. The substance is easily soluble in a dilute solution ofsodium carbonate.

EXAMPLE 2 1 part of the dyestuff No. 2 of the table given in Example 1is vatted at 4 5" C. in parts of water with the; addition of 4 parts byvolume of sodium hydroxide. solution of 3.0, per cent. strength and. 2parts. of sodium hydrosulfite. The resulting stock vat is added to asolution of 4 parts byvolume of sodium hydroxide solution of 30 per centstrengthand 2 parts of sodium hydrosulfite in 2000. parts of water. 100parts of cotton are dyed in. the resultingbath for one hour at 40-50 C.with the addition of 10 parts of sodium chloride. The cotton is thensqueezed, oxidized in the air, rinsed, acidified, again rinsed andsoaped at the boil. It is dyed yellow, and the. dyeing has goodproperties of fastness.

What is claimed is:

1. An anthraquinone vat dyestufir of the, formula The resulting solutioni .v th n heated in the.

9 i0 in which m and n represent whole numbers of at the most 7. Ananthraquinone vatdyestutf of the formula 2, R is phenylene, R1 is amember selected from the group AQNEC 0 0 o CONE consish'ng of aphenylene and diphenylene, R2 is a member selected from the groupconsisting of ---CH=CH, u n phenylene and diphenylene, and Ag isanthraquinonyl 5 bound in an u-position to the NHgro11p. in which Aq isanthraquinonyl bound inan a-position to 2. The anthraquinone vatdyestuff of the formula the -NH- group. v I

i 0 g I II 3. The anthraquinone vat dyestufi of the formula Y O a a 05 oN N I I 4. The anthraquinone vat dyestufi of the formula NH g 1 m 0 +05. The anthraquinone vat dyestufi of the formula o HN-C 00c (fi1CH=CH-CO-NBZ o IT'IH t) NH 30 20 6. The anthraquinone vat dyestuff of theformula 11 3. An'anthraquinone vat dyestufi of the formula x m co CONHAqN-HN in which Aq is anthraquinouyl bound in an lac-position to the NH-group.

Reierences-Eited in the file of this patent UNITED STATES PATENTSStilmar Mar. 22, .1949 Stilmar June 13, 1950 Stilmar -June 13, 1950Stilmar June 17, 1952 Stilmar Feb. 10, 1953 Belshaw et al Feb. 24, 1953

1. AN ANTHRAQUINONE VAT DYESTUFF OF THE FORMULA